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Ip v IP 143JOl {I/$ ASTM 06560-00 psg BS 2000-143 : 2001
Determination of asphaltenes (heptane insolublesl) incrude petroleum and petroleum products.___-_- -- _~--------- ------- ----- --
This standard does not purport to address all of the safety problerns associated with its use. It is the responsibilityof the user of this standard to establish appropriate safety and health practices and determine the applicability
of regulatory limitations prior to use.- --.
1 Scope
This standard specifies a procedure for the
determination of the heptane insoluble asphaltene
content of gas oil, diesel fuel, residual fuel oils,
lubricating oil, bitumen and crude petroleumwhich has been topped to an oil temperature of
260 “C (see A.2.1).
The prelcision is applicable to values between
0,50 ?h(M//;n) and 30,O %(m/m). Values outside
this range may stlill be valid, but may not give the
same precision values.
Oils containing additives may give erroneous
results.
2 Normative references
The following normative documents contain
provisions which, through reference in this text,
constitute provisions of this standard. For dated
references, subsequent amendments to, or
revisions of, anty of these publications do not
apply. However, p#arties to agreements based on
this standard are encouraged to investigate the
possibility of applyiing the most recent editions of
the normative documents indicated. For undated
referelnces, the latest edition of the normative
document referenced applies.
IS0 3 170, PetroJeum l iquids - Manual sampling.
IS0 3171, Petroleum l iquids - Autom atic
pipel ine samp, l ing.
IP 123, Petroleum products - Determinat ion of
dis illa iion character is t ics a t a tmospher ic
pressure. (E IS0 3405)
IP 160, Crude petroleum and l iquid petroleum
products - Laboratory determinat ion of densi ty
or re la t ive densi ty - Hydrometer method.
(= IS0 3675)
IP 365, Crude petroleum and l iquid petroleum
products - Determinat ion of den&y - QsciIJat ingU-tube meth od. (- IS0 12185)
3 Diefinitions
For the purposes of this standard, the following
definitions apply:
31asphalteneswax-free organic material insoluble in heptane,
but soluble in hot toluene.
NOTE. 1 l-lot benzene appeared in the original definitionasphaltenes, but for health reasons, this material is nolonger used. The precision of this method, when usingtoluene, has been found to be the same as when usingbenzene.
3.2crude petroleum residueresidue from distillation to an oil temperature of
260 “C carried out under the conditions of thespeciific plreparatory procedure described in annex A.
4Principle
A test portion of the sample is mixed with
heptane and the mixture heated under reflux, and
the precipitated asphaltenes, waxy substances
and inorganic material collected on a filter paper.The waxy substances are removed by washing
with hot heptane in an extractor.
After removal of the waxy substances, the
asphaltenes are separated from t,he inorga~nic
material by dissolution in hot toluene, the
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ASPHALTENES (HEPTANE INSOLUBLES), IPI
extraction
asphaltenes
solvent
weighed.
is evaporated,, the
5 Reagents and materials
51 Methylbenzene (toluene) [C,H,CH,]
Analytical reagent grade, or nitration grade.
5.2 Heptane [C,H, 6l
Analytical reagent grade.
6 Apparatus
61 General
Ground-glass joints from different sources may
have one of two diameter to length ratios. For the
purposes off this standard , either is suitable, andfor some applications, the diameter itself can be
one of two. However, it is critical that the male
and female parts of each joint is from the same
series to avoid recession or protuberance.
-5-7 DIAHOLE
6.2, Condenser
With a coil or double surface,, fitted with a 34/45
or 34/35 ground-glass joinit at the bottoim to fit
the top of the extractor. Minimum length 300 mm.
6.3 Reflux extractor
Conforming to the dimensions given in Fiigure 1.
Tolerances are k 1 mm on the height and OD of
the extractor body, and t 0,5 mm on all other
dimensions. The female ground-glass joint at the
top shall match the male ai: tlhe bottom1 of the
condenser, and the male ground-glass joint at the
bott:om shall match the female of the conical
flask.
6.4 Conical flasks
Of borosilicate glass of appropriate capacity (see
10.2 and Table I), with ground-glass joints to fit
the bottom of the extractor.
NOTE 2 Sizes 24/39, 24/29, 2 3/43 or 29/32 aresuitalble.
Figure 1 - Extractor Figure 2 - Filter paper
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ASPHALTENES (HEPTANE INSOLUBLES), IP143
6.5 Stopper
Of borosilicate glass of a size to fit the conicalflask.
6.16 Mlixer
High-speeid, non-aerating.
6.6 Evaporating vessel
Of borosilicate glass. Either a hemispherical dish
of 90 mm t 5 mm diameter, or another suitable
vessel used in conjunction with a rotovapor.
NOTE 3 A rotovapor in conjunction with a nitrogenatmosphere reduces the hazard of toluene evaporation(see 10.7)L
6.7 Filter funinel
Of borosilicate glass, 100 mm t 5 mm diameter.
7 Sampling
Unless otherwise specified, samples shall be
taken by the procedures described in IS0 3170 oris0 3171 .
8 Test Portion Preparation
81 Test portions from the laboratory samples
shall be drawn after thorough mixing and
subdivision. Heat viscous samples of residual
fuels to a temperature which renders the sample
liquid, but not above 80 “C, anid Ihomogenize
using the mixer (6.16) as necessary.
6.8 Filter papers
Whatman grade 42, 110 mm or 125 mm
diameter.
8.2 Heat samples of penetration gradebitumens to a temperature not exceeding 120 “C,
and stir well before taking an aliquot.
6.9 Analytical balance
Capable of weighing with an accuracy of 0,l mg.
8.3 Samples of hard bitumens shall be ground
to a powder before an aliquot is takern.
6.10 Forceps
Stainless steel, spade ended.
8.4 Samples of crude petroleum shall be
prepared in accordance with the procedure
descriibed in annex A, unless it is known that thiecrude petroleum contains negligible quantities of
material boiling below 80 “C.
6.1 I Timing device 9
Electronic or manual, accurate to 1 ,O s.
6.12 Oven
Capable of maintaining a temperature of 100 OC
to 110 “C.
6.13 Graduated cylinders
91 Clean all glass flasks (6.:3) and dishes
(6.6) by a means that matches the cleanliness
obtained by the use of a strongly oxidizing agent
such as ammonium peroxydisulfate iin
concentrated sulfuric acid at approximately 8 g/I,
or sulfuric: acid itself, soaking for at least 12 h,
followed Iby rinses in tap water, distilled water
and then acetone, using forceps only for handling.
50 ml and 100 mil capacity.
6.14 Stirring rods
Made of glass or polytetrafluorethylene (PTFE),
150 mlm by 3 mm diameter.
9.2 For routine analysis, use a propriletary
laboratory detergent to clean the glassware,followed by the rinses described in 10.1. When
the dletergent cleaning no longer matches the
cleanlliness required based on visual appearance,
use a strong oxidizing agent.
6.15 Coolhg vessel
Consisting of either a desiccator without
desiccant, or another suitable tightly-stoppered
vessel.
9.3 After rinsing, place the glassware in the
oven (6.12) for 30 min, and cool in the cooling
vessel (6.15) for 30 min before weighing.
Apparatus Preparation
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ASPHALTENES (HEPTANIE INSOLUBLES), IP”143
Table 1 - Test portion size, flask and heptane Volumes
Estimated asphaltene content
m/m)
Less than 0.5
0.5 to 2.0
Over 2.0 to 5.0
Over 5.0 to 10.0
Over 10.0 to 25.0
Over 25.0
Test portion sizer
c l
IO zt 2
8 t Zi
4tl
2tl
0.8 t 0.2
0.5 + 0.2
Heptane volume
ml
300 ~fr 60
240 + 60
120 I z 30
60 t 15
25 to 30
25 + 1
10 Procedure
10.1 Estimate the asphaltene content of the
sample, or residue obtained from the procedure inannex A, and weigh the quantity, to the nearest
1 mg for masses above 1 g, and to the nearest
0,l mg for masses of 1 g and below, indicated in
Table 1 into a flask (6.4) of appropriate capacity,,
also shown in Table I.
10.2 Add heptane (7.2) to the test portion
in the fllask at a ratio of 30 ml to each 1 g of
sample iif the expected asphaltene content is
below 25 %(m/m). For samples with anexpected asphaltene content of above25 %(Mm), a minimum heptane volume of 25 ml
shall be used. Table 1 also gives these values.
IO,.3 Boil the mixture under reflux for 60 min
rf: 5 min. Remove the flask and contents at theend of this period, cool, close with a stopper
(6.5), and store in a dark cupboard for 90 min to
150 min, calculated from the time of removal
f rolm ref Iux.
IO,.4 Place the filter paper, folded as shown in
Figure 2 ~(SO s to prevent loss of asphaltenes by
creeping), in the filter funnel using forceps, ,
Thereafter, handle the filter paper only with
forceps. Without agitation, decant the liquid into
the filter paper, and then transfer the residue in
the flask as completely as possible with
successive quantities of hot heptane, using the
stirring rod ( 6.14) as necessary. Give the flask a
final rinse with hot heptane and pour the rinsings
through the filter. Set the flask aside, withoutwashing, for use as specified in 11.6.
10.5 Remove the filter paper and contents from
the funnel and place in the reflux extractor (6.3).
Usiing a flask different from that used initially,
refllux with heptane (7.2) at a rate of 2 drops/s to
4 drops/s; from the end of the condenser for an
extraction period of not less than 60 min, or until
a fe w drops of heptane frorn the bottom of the
extractor leave no residue on evaporation on a
glasIs slide.
10.6 Replace the flask by the one used initially,
and to which has been added 30 ml to 6;O ml of
toluene ( 7.1), and continue refluxing until all theasphaltenes have been dissolved from the paper.
10.7 Transfer the contents of the flask to a
clealn and dry (see clause 9,) evaporating vessel
(6X), weighed to the nearest: 0,2 mg by tareagaiinst a similar dish. Wash out the fla:sk with
successive small quantities of ,toluene to a total
not exceeding 30 ml. Remove the toluene by
evaporation on a boiling water bath (see note 5),
or by evaporation in a rotovapor unider an
atmosphere of nitrogen
CAIJTION - Perform the evaporation in a fumecupboard.
10.8 Dry the dish and contents in the oven
(6.12) for 30 min. Cool in the cooling vessel
(6.15) for 30 min to 60 min and re-weigh by tare
against the dish used previously for this purpose,
and which has been subject,ed to the same
heating and cooling procedure as was the dish
containing asphaltenes.
NOTE 6 Asphaltenes are very susceptible to o:xidation,
and it is important. that the procedure specified in thefinal drying stage is adhered to exactly as regards totemperature and time.
11 Calculation
11.1 Calculate the asphaltene content, A, in %
(m/,m), of petroleum products using the equation:
A = 100 (M/G)
(1)
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ASPHALTENES (HEPTANE INSOLUBLES), IP143
where:
M is the mass of asphaltenes, ingrams;
G is the mass of test portion, ingrams.
11.2 Calculate the asphaltene content, C, in
%(m/xn), of crude petroleum prepared in themanner described in annex A, using the equation:
c = 100 (MRIGD)
(2)
where:
M
R
G
5
is the mass of asphaltenes, ingrams;
is the mass of the residue fromdistillation, in grams;
is the mass of the residue aliquot,
in grams;
is the mass of crude petroleum
sample distil led, in grams.
12 Expression of results
12.1 Report the heptane insoluble asphaltene
content of valules less than I,00 % (m/m), to the
nearest 0,05 SJa m/m), by IP 143.
12.2 Report the heptane insoluble
asphaltene content of values of I,0 % (m/m)
and greater, to the nearest 0,l % (m/m), byIP 143.
13 Precision
13.1 General
The precision values were determined in an
interlaboratory programme using benzene as
solvent in 1956. A se ond interlaboratory
programme, using toluene as solvent, was carried
out in 1975 to confirm the precision. No data
from the 1956 evaluation programme can befound.
NOTE ‘7 A recent (1998) interlaboratory programme inFrance on four samples with asphaltene contents in therange of 0,50 %(~-&m) to 22,0 %(m/m) resulted inestimated precision values very similar to those given in13.2 and 13.3,, except for the reproducibility at verylow levels [C ,T,O 9-6 (m/m)] which was significantlyworse.
13.2 Repeatability, r
The difference between two successive test
results obtained by the same operat,lor with thesame apbparatus under constant operating
conditions on identical test material would, in the
normal and correct operation of the test method,
exceed the value below only in one case intwenty.
r := 0,l A
where A is the average result, in %(m/m).
13.3 Reproducibility,
The difference between two single and
independent results obtained by different
operaltors working in different laboratories on
nominally identical test material would, in the
normal and correct operation of the test method,
exceed the value below only in one case in
twenty.
R= 0,2 A
wherle A is the average result, in ?~(m/‘lm).
13.4# Bias
Since heptane insoluble asphalten es are defined
by thlis procedure, no bias can be asisigned. The
term ‘asphaltenes’ may be associateld with othersimilar procedures using alkanes as precipitating
agents other than heptane. In genieral, light,er
alkanes will give higher results, and heavier
alkanes will give lower results than1 heptane, but
no consistent ratio can be assigned.
14 Test report
The test report shall contain at least the following
infor~mation:
a)
b)
a reference to this standard;
all details necessary for complete
identification of the product testedl;
cl
d)
the result of the test (see clause 12);
any deviation, by agreemeint or otherwise,
from the procedure specified;
e) the date of the test.
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ASPHALTENES (HEP’TANE INSOLUBLES), IP143
Annex A,normative)
Preparation of crude petroleum residue by distillation
A.1 Scope
A.1 .I This annex describes a procedure for the
preparation of a crude petroleum residue (toppedto an oil temperature of 260 “C) suitable for the
determination of asphaltene content (see 9.4).
A.2 Principle
A Iweighed test portion of the crude petroleum
sample i:s distilled in specified glass apparatus
under specified conditions of heat input and rateof distillation The distillation is stopped at an oil
temperature of 260 “C and the mass of theresidue determined.
A.3 Apparatus
A.3.1 Residue distillation apparatus
The apparatus shall conform to the requirements;
of IP 123, with the exception of the temperature
sensor.
The temperature sensor shall be a liquid-in-glass
tlhermometer of total immersion type of total
length 300 m/m to 320 mm, with a temperature
range of -4 “C to 360 “C, and a maximum scale
error of 2 “C, or an alternative temperature
meiasurement device or system of at least
equivalenit accuracy. A transparent bath,
maintained at 15 “C zt 3 “C is mandatory for the
receiver.
NOTE 8 A witable thermometer is an IP 4C.
A.3.2 Drying distillation apparatus
The apparatus shall conform to A.3.1 with theexception of a 500 ml distillation flask instead of
the flask specified, and the receiver is substituted
by a 200 ml1 separating funnel immersed in broken
ice.
A.3.3 Drying apparatus
The drying apparatus shall conisist of one of thefollowing:
A3.3. I Centrifuge
A.3.3.2 Filter apparatus, operating alt inicreasedpressure.
A.3#.3.3 Steel container, capable of withstanding
1000 kPa pressure, and of lbeing heated to 200 “C.
A.3(.3.4 Cottrell-type electro:static separator
A.4 Sample Preparation
A.4,,1 If the crude petroleum c:ontains sufficient
water to cause difficulties in distillation (ex.cessive
foaming), dry the sample by a method that avoids
the loss of volatile components. The methods
given in A.4.1.1 to A.4.1 .5 are suitable.
A.4,,1 .I Separate the water by gravity or bycentrifuging in a closed container at the lowestpracticable temperature.
A.4.J .2 Filter the sample at the lowestpracticable temperature and applied pressure,
through anhydrous calcium chloride, sodium
sulfate, or other suitable drying agent, in a closed
vessel.
A.4.1.3 Heat the sample int a closed steel
container (A.3.3) fitted with a temperature sensor
and pressure sensor. Fill the container to
approximately 70 % capacity and heat it until theoil reaches a temperature Iof 200 “C, or until the
pressure reaches 700 kPa. Allow the container to
cool to ambient temperature iand then decant the
oil from the separated water.
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ASPHALTENES (HEPTANE INSOLUBLES), IP143
A.4. II .4 Constwct a Cottrell-type separator from
a tall glass beaker with a brass gauze cylinder,lined with flannel that has been saturated with
water, and then squeezed out to leave it damp,
fitted tightly inside. A brass gauze cylindermounted on the glass spindle of a laboratory
stirrer rotated at approximately 30 rev/min forms
the central electrode. Pour the sample into thebeaker and apply a voltage to the electrodes.
Interrupt the water precipitation at intervals to
prevent the loss of volatile components and allow
the oil to cool. Separate the oil from the water
that has coalesced and run down the flannel
lining.
A.4.1.5 Distil off the water with the more volatile
hydrocarbons in the apparatus described in A.3.2.
Charge the flask with 300 ml of sample and place
the temperature sensor such that the sensing
point (bulb) is immersed in the sample. Heat the
flask gently so that the oil temperature rises
slowlly to ‘l5Q “C, vaporizing into the condenser
by means off a small gas flame, any drops of
water that collect on the walls of the flask. Stop
the distillation when no more water passes over
in the distillatle. Allow the residue to cool, run off
the water colllected in the separating funnel, and
add t,he oily distilllate back to the residue and mix
thoroughly. If visible water is still present, filter
by the method described in A.4.1.2.
A. 5 Procedure
A.5.l Determine the density at 15 “C of the
crude petroleum by IP 160 or IP 365.
A 52 Weigh the distillation flask to the nearest
0,l lg and charge it with a mass equivalent to
100 ml of sample at 15 “C to within 0,l g,
ensuring that no oil flows down the vapour tube
during this operation. Record the mass of oil (D).
Place the liquid-in-glass thermometer so that the
bottom of the bulb is 2,0 mm t 0,5 mm from
the bottom of the flask, or the alternativetemperature seinsor to a position established to
give dentical temperature readings
NOTE 9 The position of the temperature sensor in theholder may be pre-marked before addition of the testportion to the flask.
A.5.3 Swab out the condenser tub/e iandassemble the apparatus, with the vapour tube of
the flask extending into the condlenser tube a
distance of between 25 mm and 50 mm. Makethe connection between flask and condenser tight
by means of a stopper or bung through which the
vapour tube passes.
A.5.4 Place a clean dry receiver at the outlet ofthe conldenser such that the condlenser tube or
adaptor extends into it at least .25 mm, lbut not
below the 100 ml mark. Immerse the receiver up
to the 100 ml mark in the transparent biath
(A.3.1). Cover the top of the receiver closely
durilng the distillation with a piece of paper
weighted to restrict volatile losses, and also to
overcome the buoyancy of the receiver in thewater bath. Circulate ice-cold (below 4 “C) water
through the condenser.
A.5.5 Apply heat to the flask and distil the
crude petroleum at a rate not exceeding23 mllmin until it ceases to foami, after which
keep the rate of distillation constant at 2,0 ml/min
to 3 5 ml/min (approximately 1 drop/s). Continue
the-bist:illation without interruption to 260 “C.
Remove the heat and allow thie condenser to
drailn into the receiver.
A.56 Allow the residue in the ,flask to cool,
remove the temperature sensor, and weigh the
flas’k and residue. Record the mass of the residue
( R)’
AS.7 Use this residue to carry out the
proIcedwe (see clause 1 I) for the determination of
asphaltene content.
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